Water-soluble tris phenyl bisazo dyes for polyamide fibers

ABSTRACT

Disclosed are tris phenyl bisazo dyes bearing one or two sulfated alkoxycarbonyl or sulfated alkylcarbamyl groups. These dyes impart yellow to red shades to fibers, particularly polyamides, and are especially useful for dyeing polyamide (nylon) carpets, generally giving good fastness to light, ozone, oxides of nitrogen, washing, sublimation, crocking, and the like, and having good leveling, exhaustion, build properties, and stability to variations in dyeing condition such as pH and temperature. 
     The present dyes have the general formula: ##STR1## wherein X is --O--, --NH--, --N(alkyl)--, or --N(aryl)--; Z is selected from straight or branched-chain alkylene, and such alkylene containing one or two internal linkages independently selected from ether, amine and amide; M is H, Na, K, or NH 4  ; n is 1 or 2; R 3  is --OH, alkoxy or --NR 8  R 9 , wherein R 8  and R 9  are independently selected from H and alkyl and when either R 4  or R 5  is hydroxy or alkoxy ortho to the azo radical, R 3  is further selected from hydrogen, halogen, alkyl, aryl and acylamido; and R, R 1 , R 2 , R 4 , and R 5  are independently selected from hydrogen, halogen, hydroxyl, alkyl, aryl, alkoxy, and acylamido, with the proviso that when R 3  is neither --OH, alkoxy, nor --NR 8  R 9 , one of R 4  and R 5  is either hydroxy or alkoxy ortho to the azo radical. These alkyl, alkylene, alkoxy and aryl moieties may be substituted with a wide variety of substituents known to the art.

Disclosed are bisazo dyes bearing one or two sulfated alkoxycarbonyl orsulfated alkylcarbamyl groups. These dyes are water-soluble exhibitingexcellent dyeing properties on polyamide fibers and also are useful fordyeing cellulose acetate and wool. The dyes have the general formula:##STR2## wherein X is --O--, --NH--, --N(alkyl)--, or --N(aryl)--; Z isselected from straight or branched-chain alkylene, and such alkylenecontaining one or two internal linkages independently selected fromether, amine and amide; M is H, Na, K, or NH₄ ; n is 1 or 2; R₃ is --OH,alkoxy or --NR₈ R₉ wherein R₈ and R₉ are independently selected from Hand alkyl and when either R₄ or R₅ is hydroxy or alkoxy ortho to the azoradical, R₃ is further selected from hydrogen, halogen, alkyl, aryl andacylamido; and R, R₁, R₂, R₄, and R₅ are the same or different groupsselected from hydrogen, halogen, hydroxyl, alkyl, aryl, alkoxy, andacylamido, with the proviso that when R₃ is neither --OH, alkoxy, nor--NR₈ R₉, one of R₄ and R₅ is either hydroxy or alkoxy ortho to the azoradical. These alkyl, alkylene, alkoxy and aryl moieties may besubstituted with one to three substituents selected from hydroxy,halogen, cyano, succinimido, cyclohexyl, alkylsulfonyl, alkylthio,alkanoyl, alkanoyloxy, amino, alkylamino, dialkyl-amino, arylamino,furyl, alkoxy, phenoxy, alkanoylamino, sulfamoyl, alkylsulfamoyl,dialkylsulfamoyl, phenyl and phenyl substituted with alkyl, alkoxy,halogen, alkanoyl-amino, cyano or alkoxycarbonyl, --COOR⁶ wherein R⁶ isselected from alkyl and alkyl substituted with halogen, hydroxy,phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxyor alkoxy, and OCOR⁷ wherein R⁷ is alkyl. All of the above alkyl,alkylene, alkoxy and aryl moieties contain from one to six carbons.

These dyes impart yellow to red shades to fibers, particularlypolyamides, and are especially useful for dyeing polyamide (nylon)carpets, generally giving good fastness to light, ozone, oxides ofnitrogen, washing, sublimation, crocking, and the like, and having goodleveling, exhaustion, build properties, and stability to variations indyeing condition such as pH and temperature.

The dyes bearing sulfated alkylcarbamyl groups may be prepared byreacting a diazotizable coupler (B--NH₂) with the diazonium salt of abenzene compound (ring A) which contains one or two carbalkoxy groups.The resulting monoazo dye A--N═N--B--NH₂ is diazotized and coupled withan ortho or para-coupling moiety such as a phenol (C--OH). The phenolicgroup on ring C may be treated subsequently, for example, with an alkylhalide or dialkyl sulfate to alkylate the phenolic group of ring C.Anytime after the first coupling reaction, the carbalkoxy group of ringA can be reacted with an amino alcohol H₂ N--Z--OH (Z is alkylene) toconvert it to a N-(hydroxyalkyl)carbamyl group and then withconcentrated sulfuric acid to sulfate the hydroxyl group. An exemplarysequence of these reactions is illustrated as follows: ##STR3##

The dyes bearing sulfated alkoxycarbonyl groups (COO--Z--OSO₃ H) areprepared, for example, from an aniline compound (A--NH₂) containing oneor two hydroxyalkoxy carbonyl groups. As above, the aniline compound isdiazotized, coupled with B--NH₂, diazotized again, then coupled withC--OH and, if desired, alkylated on the phenolic group of the thirdring. Reaction with concentrated sulfuric acid to form the sulfate ofthe hydroxyalkoxy carbonyl group may be performed either before thefirst diazotization or at any time thereafter. The dyes are customarilyisolated in the form of the alkali salt.

This invention will be further illustrated by the following exampleswhich are included merely for purposes of illustration and are notintended to limit the scope of the invention.

EXAMPLE 1

Methyl anthranilate (30.23 g) is diazotized at 0°-2° C. by dissolving itin dilute hydrochloric acid (60 ml of 37% HCl in 200 ml of water) andadding sufficient sodium nitrite solution (14.4 g of NaNO₂ in 40 ml ofwater) to the anthranilate solution over a period of 45-50 minutes. Thediazotized material preferably is allowed to stand at about 2° C. forone-half hour longer before being used.

Approximately one fifth of a mole of 2-methoxy-5-methylaniline isdissolved in a solution of 700 ml of 1:5 acid (1:5 ratio by volume ofpropionic/acetic) and 150 ml of 15% sulfuric acid, the solution cooledto 0° C. and held at 0°-3° C. while the diazonium solution is addedthereto. About 70 g of sodium acetate is also added in portions to makethe material neutral to Congo Red.

After an additional hour at about 2° C., 500 ml of concentrated ammoniumhydroxide (28% NH₃) is added at such a rate that the temperature doesnot exceed 25° C. As the pH increases toward neutral, the productappears as an oil, then as crystals or pellets which are removed byfiltration, washed with water and recrystallized from dilute methanol.The yellow product is 4-[(2-carbomethoxyphenyl)azo]-2-methoxy-5methylaniline having a λ max. in acetone at 419 nm.

EXAMPLE 2

9.46 Grams of the product of Example 1 is dissolved in a solution of 3ml of concentrated hydrochloric acid and 9 ml of acetic acid in 34 ml ofwater. A solution of 6 ml of concentrated hydrochloric acid in 60 g ofice and water is added first, followed by a solution of 2.16 g of sodiumnitrite in 7 ml of water, all within several minutes. The temperaturerises to about 15° C. and then to about 20° C. after a further 2.5 hoursat room temperature.

A coupler solution consisting of 2.82 g of phenol dissolved in 100 ml ofwater containing 4.38 g of 98% sodium hydroxide is cooled with ice tomaintain a temperature of about 0° C., and the above diazonium solutionadded thereto to bring the total volume to about 400 ml. The productsolidifies over night and is readily filterable. The λ max. in acetoneis at 405 nm. and the product is4'-[(2"-carbomethoxyphenyl)azo]-5'-methyl-2'-methoxy-4-hydroxy-azo-benzene.

EXAMPLE 3

A 4.00 g portion of the product of Example 2 is added to a solution of10 ml of ethanolamine and 5 ml of isopropanol. The solution is heated bysteam for 40 minutes and poured into a solution of 10 ml of acetic acidin 30 ml of water and the product was removed by filtration.Recrystallization is from hot, dilute isopropanol to remove someunreacted material. The λ max. in acetone is at 418 nm. The product isthe disperse dye4'-[(2"-N-hydroxyethylcarbamylphenyl)-azo]-5'-methyl-2'-methoxy-4-hydroxy-azo-benzene.

EXAMPLE 4

The product of Example 3 is sulfated in concentrated sulfuric acid,using 2.00 g of intermediate for 10 ml of sulfuric acid, and using abath of ice water to prevent overheating. The solution is added to about35 g of ice and the precipitate removed by filtration, slurried in coldwater, and refiltered. The wet precipitate is treated with dilute sodiumhydroxide solution until soluble, then with acetic acid untilreprecipitated at about pH 6. The product is removed by filtration anddried at 60° C. The product is4'-[(2"-N-sulfatoethyl-carbamylphenyl)azo]-5'-methyl-2'-methoxy-4-hydroxy-azobenzene,Na salt. The λ max. in aqueous acetone is at 522 nm. and the acid dye isyellow-orange with good properties on nylon 6 tricot fabric and nylon6.6 carpet.

EXAMPLE 5

Approximately one gram of the product of Example 3 is treated in basicsolution (25 ml) with about five grams of diethyl sulfate at 80°-90° C.The basic solution is made from 5 g of soldium bicarbonate in 100 ml ofwater, with sufficient 25% sodium hydroxide solution to increase the pHto about 11. The diethyl sulfate is added dropwise during about twohours, along with sufficient 25% sodium hydroxide solution to maintainthe pH at 11. The product is recovered by filtration after dilution ofthe reaction system with water and cooling with ice. The productconsists of the disperse dye4'-[(2"-N-hydroxyethylcarbamyl-phenyl)azo]-2'-methyl-2'-methoxy-4-ethoxy-azobenzene,having λ max. in acetone at 408 mm.

EXAMPLE 6

About one-third gram of the product of Example 5 is dissolved in justenough concentrated sulfuric acid (2-3 ml) to dissolve it readily atroom temperature. The solution is added to sufficient ice to keep thetemperature below 20° C. as the solution is made basic with sodiumhydroxide solution. The product is removed by filtration and washed with15% sodium sulfate solution. The product is the acid dye4'[(2"-N-sulfoethylcarbamylphenyl)azo]-5'-methyl-2'-methoxy-4-ethoxy-azo-benzene,Na salt having a λ max. at 413 nm and thus imparting to nylon fibers anorange shade less reddish than the dye of Example 4. The dye exhibitsgood properties such as lightfastness on both nylon 6 tricot fabric andnylon 6.6 carpet and shows good exhaustion, build, and migration onnylon carpet.

Additional examples illustrating the compounds of the present inventionare given in the table below. In Examples 7-56, the acid groupCO--X--Z--OSO₃ M is located at position 2".

    __________________________________________________________________________     ##STR4##                                                                 

    __________________________________________________________________________    Ex.                                                                           No.                                                                              XZ              M  R    R.sub.1                                                                              R.sub.2                                     __________________________________________________________________________     7 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                             Na H    H      H                                            8 NHCH.sub.2 CH.sub.2                                                                           Na H    H      H                                            9 NHCH.sub.2 CH.sub.2                                                                           Na H    H      H                                           10 NHCH.sub.2 CH.sub.2                                                                           Na H    H      H                                           11 NHCH.sub.2 CH.sub.2                                                                           K  H    H      H                                           12 NHCH.sub.2 CH.sub.2                                                                           K  H    3'-CH.sub.3                                                                          5'-CH.sub.3                                 13 NHCH.sub.2 CH.sub.2                                                                           Na H    H      H                                           14 N(CH.sub.3)CH.sub.2 CH.sub.2                                                                  Na 4"-Br                                                                              H      H                                           15 OCH.sub.2 CH.sub.2                                                                            Na H    H      H                                           16 NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                            Na 4"-Cl                                                                              H      H                                           17 NHCH.sub.2 CH.sub.2                                                                           Na H    H      5'-NHCOCH.sub.3                             18 NHCH.sub.2 CH.sub.2                                                                           Na H    H      5'-NHCOCH.sub.3                             19 NHCH.sub.2 CH.sub.2                                                                           K  4"-OH                                                                              2'-Cl  H                                           20 NHCH.sub.2 CH.sub.2                                                                           K  H    2'-Cl  H                                           21 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-CH.sub.3                                                                          H                                           22 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-CH.sub.3                                                                          H                                           23 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-CH.sub.3                                                                          H                                           24 NHCH.sub.2 CH.sub.2                                                                           Na 6"-Br                                                                              3'-CH.sub.3                                                                          H                                           25 NHCH.sub.2 CH.sub.2                                                                           Na 6"-Br                                                                              3'-CH.sub.3                                                                          H                                           26 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-CH.sub.3                                                                          H                                           27 NHC.sub.2 H.sub.4 NHC.sub.2 H.sub.4                                                           K  H    3'-CH.sub.3                                                                          H                                           28 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                             Na H    3'-CH.sub.3                                                                          H                                           29 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                             Na H    H      H                                           30 NHCH.sub.2 CH(CH.sub.3)CH.sub.2                                                               Na H    3'-OCH.sub.3                                                                         H                                           31 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-OCH.sub.3                                                                         H                                           32 OCH.sub.2 CHClCH.sub.2                                                                        K  5"-Br                                                                              3'-OCH.sub.3                                                                         H                                           33 NHCH.sub.2 CH.sub.2                                                                           K  H    3'-OCH.sub.3                                                                         H                                           34 OCH.sub.2 CH.sub.2                                                                            NH.sub.4                                                                         H    3'-OCH.sub.3                                                                         H                                           35 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-OC.sub.2 H.sub.5                                                                  H                                           36 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-NHCOCH.sub.3                                                                      H                                           37 NHCH.sub.2 CH.sub.2                                                                           Na 6"-Cl                                                                              2'-Br  5'-Br                                       38 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-CH.sub.3                                                                          5'-CH.sub.3                                 39 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-CH.sub.3                                                                          5'-CH.sub.3                                 40 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-CH.sub.3                                                                          5'-CH.sub.3                                 41 NHC.sub.2 H.sub.4 CONHC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                        NH.sub.4                                                                         4"-Br                                                                              2'-CH.sub.3                                                                          5'-CH.sub.3                                 42 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-CH.sub.3                                                                          5'-CH.sub.3                                 43 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-CH.sub.3                                                                          5'-CH.sub.3                                 44 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-CH.sub.3                                                                          5'-CH.sub.3                                 45 NHCH.sub.2 CH.sub.2 CH.sub.2                                                                  Na H    2'-CH.sub.3                                                                          5'-CH.sub.3                                 46 NHCH.sub.2 CH.sub.2 CH.sub.2                                                                  Na H    2'-CH.sub.3                                                                          5'-CH.sub.3                                 47 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-CH.sub.3                                                                          5'-CH.sub.3                                 48 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-CH.sub.3                                                                          5'-OCH.sub.3                                49 OCH.sub.2 CH.sub.2                                                                            NH.sub.4                                                                         H    2'-CH.sub.3                                                                          5'-OCH.sub.3                                50 NHCH.sub.2 CH.sub.2                                                                           K  H    2'-CH.sub.3                                                                          5'-OCH.sub.3                                51 NHCH.sub.2 CH.sub.2                                                                           K  H    2'-CH.sub.3                                                                          5'-NHCOCH.sub.3                             52 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-CH.sub.3                                                                          5'-NHCOCH.sub.3                             53 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-OCH.sub.3                                                                         5'-OCH.sub.3                                54 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-OCH.sub.3                                                                         5'-OCH.sub.3                                55 OCH.sub.2 C(CH.sub.3).sub.2 CH.sub.2                                                          Na H    2'-OCH.sub.3                                                                         5'-OCH.sub.3                                56 NHCH.sub.2 C(CH.sub.3).sub.2 CH.sub.2                                                         NH.sub.4                                                                         H    2'-OCH.sub.3                                                                         5'-OCH.sub.3                                57 NHCH.sub.2 CHCl Na H    H      H                                           58 NHCH.sub.2 CHCl Na H    H      5'-C.sub.2 H.sub.4 CN                       59 NHCH.sub.2 CHCl K  H    H      H                                           60 NHCH.sub.2 CHCl K  H    3'-OH  5'-OH                                       61 OCH.sub.2 CH.sub.2                                                                            K  H    3'-CH.sub.2 C.sub.6 H.sub.5                                                          H                                           62 NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                            K  4"-Cl                                                                              H      H                                           63  NHCH(C.sub.6 H.sub.11)CH.sub.2                                                               K  H    H      5'-NHCOCH.sub.3                             64 NHCH.sub.2 CH.sub.2                                                                           K  4"-OH                                                                              2'-Cl  H                                           65 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-CH.sub.2 Cl                                                                       H                                           66 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-CH.sub.2 Cl                                                                       5'-OCH.sub.2 Br                             67 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-CH.sub.2 Cl                                                                       H                                           68 NHCH.sub.2 CH.sub.2                                                                           Na 6"-Br                                                                              3'-CH.sub.2 CN                                                                       H                                           69 NHCH.sub.2 CH.sub.2                                                                           Na 6"-Br                                                                              3'-CH.sub.3                                                                          H                                           70 NHCH.sub.2 CH.sub.2                                                                           Na H    3'-CH.sub.3                                                                          H                                           71 NHC.sub.2 H.sub.4 NHC.sub.2 H.sub.4                                                           K  4"-C.sub.2 H.sub.5                                                                 3'-CH.sub.3                                                                          H                                           72 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                             Na H    3'-CH.sub.2 OH                                                                       H                                           73 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                             Na H    H      H                                           74 NHCH.sub.2 CH(CH.sub.3)CH.sub.2                                                               Na H    3'-OCH.sub.3                                                                         H                                           75 NHCHClCH.sub.2  Na H    3'-OCH.sub.3                                                                         H                                           76 NHCH.sub.2 CH.sub.2                                                                           Na 5"-OCH.sub.3                                                                       3'-OCH.sub.3                                                                         H                                           77 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-CH.sub.2 OC.sub.2 H.sub.5                                                         5'-CH.sub.3                                 78 NHC.sub.2 H.sub.4 CONHC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                        NH.sub.4                                                                         4'-Br                                                                              H      5'-CH.sub.3                                 79 NHCH(C.sub.6 H.sub.5)CH.sub.2                                                                 K  H    H      5'-CH.sub.3                                 80 NHCH.sub.2 CH.sub.2                                                                           K  H    H      5'-NHCOCH.sub.3                             81 NHCH.sub.2 CH.sub.2                                                                           Na H    H      5'-NHCOCH.sub.3                             82 NHCH.sub.2 CH.sub.2                                                                           Na H    2'-OCH.sub.3                                                                         5'-OCH.sub.2 COOCH.sub.3                    __________________________________________________________________________                   Ex.                                                                           No.                                                                              R.sub.3 R.sub.4 R.sub.5                                     __________________________________________________________________________                    7 OH      H       H                                                           8 OCH.sub.3                                                                             5-CH.sub.3                                                                            H                                                           9 OC.sub.2 H.sub.5                                                                      5-CH.sub.3                                                                            H                                                          10 OH      2-CH.sub.3                                                                            H                                                          11 OH      5-CH.sub.3                                                                            H                                                          12 OH      H       H                                                          13 OH      3-CH.sub.3                                                                            H                                                          14 OH      5-C.sub.2 H.sub.5                                                                     H                                                          15 OH      2-CH.sub.3                                                                            H                                                          16 OH      H       5-OH                                                       17 OH      H       H                                                          18 OC.sub.2 H.sub.5                                                                      H       H                                                          19  OH     H       H                                                          20 OH      2-C.sub.2 H.sub.5                                                                     H                                                          21 OH      H       H                                                          22 OH      2-Cl    H                                                          23 OC.sub.2 H.sub.5                                                                      2-Cl    H                                                          24 OC.sub.2 H.sub.5                                                                      2-OH    H                                                          25 OC.sub.2 H.sub.5                                                                      3-CH.sub.3                                                                            H                                                          26 H       2-CH.sub.3                                                                            6-OCH.sub.3                                                27 H       2-OCH.sub.3                                                                           5-CH.sub.3                                                 28 OC.sub.2 H.sub.5                                                                      3-CH.sub.3                                                                            5-CH.sub.3                                                 29 OH      2-CH.sub.3                                                                            6-CH.sub.3                                                 30 OH      2-C.sub.2 H.sub.5                                                                     H                                                          31 OH      H       H                                                          32 OC.sub.2 H.sub.5                                                                      2-CH.sub.3                                                                            H                                                          33 OC.sub.2 H.sub.5                                                                      2-OCH.sub.3                                                                           H                                                          34 OC.sub.2 H.sub.5                                                                      2-Cl    H                                                          35 OC.sub.2 H.sub.5                                                                      2-CH.sub.3                                                                            6-CH.sub.3                                                 36 OC.sub.2 H.sub.5                                                                      2-CH.sub.3                                                                            H                                                          37 OC.sub.2 H.sub.5                                                                      H       H                                                          38 OCH.sub.3                                                                             H       H                                                          39 OCH.sub.3                                                                             3-CH.sub.3                                                                            H                                                          40 OCH.sub.3                                                                             2-CH.sub.3                                                                            H                                                          41 OCH.sub.3                                                                             2-CH.sub.3                                                                            6-CH.sub.3                                                 42 OCH.sub.3                                                                             2-CH.sub.3                                                                            5-CH.sub.3                                                 43 OCH.sub.3                                                                             3-CH.sub.3                                                                            5-CH.sub.3                                                 44 OH      3-CH.sub.3                                                                            5-CH.sub.3                                                 45 OH      2-CH.sub.3                                                                            H                                                          46 OH      2-CH.sub.3                                                                            6-CH.sub.3                                                 47 OH      2-CH.sub.3                                                                            5-CH.sub.3                                                 48 OH      H       H                                                          49 OC.sub.2 H.sub.5                                                                      H       H                                                          50 OCH.sub.3                                                                             H       H                                                          51 OH      2-CH.sub.3                                                                            6-CH.sub.3                                                 52 OH      2-CH.sub.3                                                                            6-CH.sub.3                                                 53 OH      5-CH.sub.3                                                                            H                                                          54 OH      2-Cl    H                                                          55 OH      2-CH.sub.3                                                                            6-CH.sub.3                                                 56 OH      3-CH.sub.3                                                                            5-CH.sub.3                                                 57 OCH.sub.2 Cl                                                                          5-CH.sub.3                                                                            H                                                          58 OC.sub.2 H.sub.5                                                                      5-CH.sub.3                                                                            H                                                          59 OH      5-CH.sub.2 Cl                                                                         H                                                          60 OH      H       H                                                          61 OH      2-CH.sub.3                                                                            H                                                          62 OH      H       5-OH                                                       63 OH      H       H                                                          64 OH      H       5-C.sub.2 H.sub.4 OCOCH.sub.3                              65 OH      H       H                                                          66 OH      2-Cl    H                                                          67 OC.sub.2 H.sub.4 C.sub.6 H.sub.11                                                     2-Cl    H                                                          68 OC.sub.2 H.sub.4 C.sub.6 H.sub.11                                                     2-OH    H                                                          69 OC.sub.2 H.sub.4 C.sub.6 H.sub.11                                                     3-CH.sub.3                                                                            H                                                          70 H       2-OCH.sub.3                                                                           6-CH.sub.2 Cl                                              71 H       2-OCH.sub.3                                                                           5-CH.sub.3                                                 72 OC.sub.2 H.sub.5                                                                      3-CH.sub.3                                                                            5-CH.sub.3                                                 73 OH      2-CH.sub.2 CN                                                                         6-CH.sub.3                                                 74 OH      2-C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                    H                                                          75 OH      H       H                                                          76 OH      2-OCH.sub.3                                                                           H                                                          77 OCH.sub.3                                                                             H       H                                                          78 OC.sub.2 H.sub.4 OCH.sub.3                                                            H       6-CH.sub.3                                                 79 OCH.sub.3                                                                             H       H                                                          80 OH      2-C.sub.2 H.sub.4 OCH.sub.3                                                           6-CH.sub.3                                                 81 OH      2-C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                    6-CH.sub.3                                                 82 OH      5-CH.sub.3                                                                            H                                           __________________________________________________________________________

In Examples 83-88, the acid group is located at position 3":

    __________________________________________________________________________    83                                                                              --OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 --                                                  K H   H    H      --OH H   H                                      84                                                                              --NHCH.sub.2 CH.sub.2 --                                                                Na                                                                              H   H    H      --OH 3-C.sub.2 H.sub.5                                                                 H                                      85                                                                              --NHCH.sub.2 CH.sub.2 --                                                                Na                                                                              H   H    5'-NHCOCH.sub.3                                                                      --OC.sub.2 H.sub.5                                                                 H   H                                      86                                                                              --NHCH.sub.2 CH.sub.2 --                                                                Na                                                                              H   3'-CH.sub.3                                                                        H      --OH H   H                                      87                                                                              --NHCH.sub.2 CH.sub.2 --                                                                Na                                                                              4"-Cl                                                                             3'-OCH.sub.3                                                                       H      --OC.sub.2 H.sub.5                                                                 H   H                                      88                                                                              --NHCH.sub.2 CH.sub.2 --                                                                Na                                                                              H   2'-OCH.sub.3                                                                       5'-OCH.sub.3                                                                         --OH 5-CH.sub.3                                                                        H                                      __________________________________________________________________________

In Examples 89-96, the acid group is located at position 4":

    __________________________________________________________________________    89 --NHCH.sub.2 CH.sub.2 --                                                                    K  2"-Br                                                                             2'-CH.sub.3                                                                        5'-CH.sub.3                                                                       --OC.sub.2 H.sub.5                                                                 H   H                                   90 --NHCH.sub.2 CH.sub.2 --                                                                    Na H   2'-CH.sub.3                                                                        5'-CH.sub.3                                                                       --OC.sub.2 H.sub.5                                                                 2-Cl                                                                              H                                   91 --NHCH.sub.2 CH.sub.2 --                                                                    Na H   2'-CH.sub.3                                                                        5'-CH.sub.3                                                                       --OC.sub.2 H.sub.5                                                                 3-CH.sub.3                                                                        5-CH.sub.3                          92 --OCH.sub.2 CH.sub.2 --                                                                     Na H   2'-Br                                                                              5'-Br                                                                             --OH H   H                                   93 --NHCH.sub.2 CH.sub.2 CH.sub.2 --                                                           NH.sub.4                                                                         3"-Br                                                                             3'-OCH.sub.3                                                                       H   --OH 2-CH.sub.3                                                                        5-CH.sub.3                          94 --OCH.sub.2 CH(OSO.sub.3 Na)CH.sub.2 --                                                     Na H   3'-OCH.sub.3                                                                       H   --OH 3-CH.sub.3                                                                        5-CH.sub.3                          95 --NHCH.sub.2 CH.sub.2 --                                                                    Na H   2'-OCH.sub.3                                                                       5'-CH.sub.3                                                                       --OCH.sub.3                                                                        H   H                                   96 --NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 --                                                     K  H   2'-OCH.sub.3                                                                       5'-CH.sub.3                                                                       --OC.sub.2 H.sub.5                                                                 H   H                                   __________________________________________________________________________

In Examples 97-101, n=2, and the acid groups are located at positions 2"and 3":

    __________________________________________________________________________    97 --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H 2'-OCH.sub.3                                                                       5'-CH.sub.3                                                                       --OH    H   H                                      98 --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H 2'-OCH.sub.3                                                                       5'-CH.sub.3                                                                       --OCH(CH.sub.3).sub.2                                                                 H   H                                      99 --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H 3'-CH.sub.3                                                                        H   --OH    H   H                                      100                                                                              --NHCH.sub.2 CH.sub.2 CH.sub.2 --                                                        Na                                                                              H 3'-CH.sub.3                                                                        H   --OCH.sub.3                                                                           2-CH.sub.3                                                                        H                                      101                                                                              --OCH.sub.2 CH.sub.2 --                                                                  Na                                                                              H 2'-CH.sub.3                                                                        5'-CH.sub.3                                                                       --OC.sub.2 H.sub.5                                                                    H   H                                      __________________________________________________________________________

In Examples 102-106, n=2, and the acid groups are located at positions3" and 5":

    __________________________________________________________________________    102                                                                              --NHCH.sub.2 CH.sub.2 --                                                                Na H  H    H  --OH H   H                                         103                                                                              --NHCH.sub.2 CH.sub.2 --                                                                Na H  H    H  --OC.sub.2 H.sub.5                                                                 H   H                                         104                                                                              --NHCH.sub.2 CH.sub.2 --                                                                K  H  3'-CH.sub.3                                                                        H  --OH H   H                                         105                                                                              --NHCH.sub.2 CH.sub.2 --                                                                NH.sub.4                                                                         H  3'-CH.sub.3                                                                        H  --OC.sub.2 H.sub.5                                                                 H   H                                         106                                                                              --OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 --                                                  Na H  3'-OCH.sub.3                                                                       H  --OCH.sub.3                                                                        5-CH.sub.3                                                                        H                                         __________________________________________________________________________

In Examples 107-122, n=1, and the acid groups are located at position2".

    __________________________________________________________________________    107                                                                              --OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                      Na                                                                              H   H   H      --NH.sub.2                                                                              H      H                             108                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H   H   H      --NHC.sub.2 H.sub.5                                                                     2-CH.sub.3                                                                           H                             109                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H   H   H      --N(C.sub.2 H.sub.5).sub.2                                                              2-CH.sub.3                                                                           H                             110                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H   H   H      --NHC.sub.2 H.sub.4 OH                                                                  2-CH.sub.3                                                                           H                             111                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 K H   H   H      --N(CH.sub.2 CH.sub.2 Cl).sub.2                                                         2-CH.sub.3                                                                           H                             112                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 K H   3'-OH                                                                             5'-OH  --NHCH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                   OCH.sub.3                                                                            H                             113                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H   H   H      --N(C.sub.2 H.sub.5).sub.2                                                              NHCOCH.sub.3                                                                         H                             114                                                                              --N(CH.sub.3)CH.sub.2 CH.sub.2 --                                                        Na                                                                              4"-Br                                                                             H   H      --N(C.sub.2 H.sub.5).sub.2                                                              Cl     H                             115                                                                              --OCH.sub.2 CH.sub.2 --                                                                  Na                                                                              H   H   H      -- N(C.sub.2 H.sub.5).sub.2                                                             2-CH.sub.3                                                                           5-CH.sub.3                    116                                                                              --NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 --                                                  Na                                                                              4"-Cl                                                                             H   H      --N(C.sub.2 H.sub.5).sub.2                                                              2-C.sub.2 H.sub.5                                                                    5-CH.sub.3                    117                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H   H   5'-NHCOCH.sub.3                                                                      --N(C.sub.2 H.sub.5).sub.2                                                              2-Cl   5-CH.sub.3                    118                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H   H   5'-NHCOCH.sub.3                                                                      --N(C.sub.2 H.sub.5).sub.2                                                              2-CH.sub.3                                                                           5-OCH.sub.3                   119                                                                              --NHCH.sub.2 CH.sub.2                                                                    K 4"-OH                                                                             2'-Cl                                                                             H      --N(C.sub.2 H.sub.5).sub.2                                                              2-NHCOCH.sub.3                                                                       5-CH.sub.3                    120                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 K H   2'-Cl                                                                             H      --NHC.sub.2 H.sub.5                                                                     2-NHCOCH.sub.3                                                                       5-CH.sub.3                    121                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H   3'-CH.sub.3                                                                       H      --NHC.sub.4 H.sub.9 --n                                                                 2-CH.sub.3                                                                           5-OCH.sub.3                   122                                                                              --NHCH.sub.2 CH.sub.2 --                                                                 Na                                                                              H   3'-CH.sub.3                                                                       H      --NHCH.sub.3                                                                            2-NHCOCH.sub.3                                                                       5-CH.sub.3                    __________________________________________________________________________

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. A dye of the formula: ##STR5## wherein X is --O--, --NH--,--N(alkyl)--, or --N(aryl)--; Z is selected from straight orbranched-chain alkylene, --C₂ H₄ --O--C₂ H₄ --, --C₂ H₄ CONHC₂ H₄ OC₂ H₄--, and --C₂ H₄ NHC₂ H₄ --; M is H, Na, K or NH₄ ; n is 1 or 2; R₃ is--OH, alkoxy or --NR₈ R₉ wherein R₈ and R₉ are independently selectedfrom H and alkyl and when either R₄ or R₅ is hydroxy or alkoxy ortho tothe azo radical, R₃ is further selected from hydrogen, halogen, alkyl,and aryl; R, R₁, R₂, R₄, and R₅ are the same or different groupsselected from hydrogen, halogen, hydroxyl, alkyl, aryl, alkoxy andalkanoylamino; with the proviso that when R₃ is neither --OH, alkoxy,nor --NR₈ R₉, one of R₄ and R₅ is either hydroxy or alkoxy ortho to theazo radical; and wherein these alkyl, alkylene, alkoxy and aryl moietiesare unsubstituted or substituted with one to three substituents selectedfrom hydroxy, halogen, cyano, succinimido, cyclohexyl, alkyl-sulfonyl,alkylthio, alkanoyl, alkanoyloxy, amino, alkylamino, dialkylamino,arylamino, furyl, alkoxy, phenoxy, alkanoylamino, sulfamoyl,alkylsulfamoyl, dialkylsulfamoyl, phenyl and phenyl substituted withalkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl, --COOR⁶wherein R⁶ is selected from alkyl and alkyl substituted with halogen,hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio,alkanoyloxy or alkoxy, and OCOR⁷ wherein R⁷ is alkyl.
 2. The dyeaccording to claim 1 of the formula: ##STR6##
 3. The dye according toclaim 1 of the formula: ##STR7##
 4. The dye according to claim 1 of theformula: ##STR8##
 5. The dye according to claim 1 of the formula:##STR9##
 6. The dye according to claim 1 of the formula: ##STR10##